CN107162968A - A kind of method of visible light catalytic Tetrahydroquinolinesas oxidative dehydrogenation synthesis of quinoline class compound - Google Patents

A kind of method of visible light catalytic Tetrahydroquinolinesas oxidative dehydrogenation synthesis of quinoline class compound Download PDF

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CN107162968A
CN107162968A CN201710377981.5A CN201710377981A CN107162968A CN 107162968 A CN107162968 A CN 107162968A CN 201710377981 A CN201710377981 A CN 201710377981A CN 107162968 A CN107162968 A CN 107162968A
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tetrahydroquinolinesas
visible light
phenyl
oxidative dehydrogenation
quinoline
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CN107162968B (en
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薛东
吉震飞
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Shaanxi Normal University
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Shaanxi Normal University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
    • C07D215/06—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms having only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to the ring nitrogen atom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/12—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/12—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D215/14—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/18—Halogen atoms or nitro radicals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
    • B01J2231/76—Dehydrogenation
    • B01J2231/766—Dehydrogenation of -CH-CH- or -C=C- to -C=C- or -C-C- triple bond species

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

The invention discloses a kind of method of visible light catalytic Tetrahydroquinolinesas oxidative dehydrogenation synthesis of quinoline class compound, this method substitutes peroxide as oxidant, polysubstituted BODIPY organic compounds by the use of oxygen and is used as photochemical catalyst, catalysis 1,2,3,4 Tetrahydroquinolinesas oxidative dehydrogenation synthesis of quinoline class compounds, compared with existing synthetic method, reaction condition is gentle, used in reaction without metal photocatalysts, catalyst amount is few, high catalytic efficiency, stability and high efficiency, it is simple to operate, environment-friendly, product yield is high, and selectivity is good.

Description

A kind of visible light catalytic Tetrahydroquinolinesas oxidative dehydrogenation synthesis of quinoline class chemical combination The method of thing
Technical field
The present invention relates to one kind under the conditions of radiation of visible light, using the organic photochemical catalyst efficient catalytics of polysubstituted BODIPY The method of Tetrahydroquinolinesas and its derivative oxidative dehydrogenation synthesis of quinoline class compound.
Background technology
Quinolines are widely used in the fields such as synthetic drug, natural products, synthetic material, in organic synthesis Learn in research, develop a kind of method for efficiently synthesizing quinolines significant.Reported by tetrahydroquinoline The method of class compound direct dehydrogenation synthesis of quinoline class compound can be divided into two classes, under the conditions of a class is anaerobic agent, iridium (Yamaguchi,R.；Ikeda,C.；Takahashi,Y.；Fujita,K.J.Am.Chem.Soc.2009,131,8410； Fujita,K.；Tanaka,Y.；Kobayashi,M.；Yamaguchi, R.J.Am.Chem.Soc.2014,136,4829.), iron (Chakraborty,S.；Brennessel,W.W.；Jones, W.D.J.Am.Chem.Soc.2014,136,8564.), ruthenium (Muthaiah,S.；Hong, S.H.Adv.Synth.Catal.2012,354,3045.) etc. metal complex catalyzed dehydrogenation.Separately One class is that have oxidant to participate in oxidative dehydrogenation, and 2014, Shannon S.Stahl seminars were reported under Oxygen Condition, Ru- Metal complex catalyzed dehydrogenation synthesis of quinoline class compound (Wendlandt, the A.E. of Co；Stahl, S.S.J.Am.Chem.Soc.2014,136,11910.).2015, Matthias Beller seminars, which report, utilized iron oxygen Compound is carried on the heterogeneous catalysis FeOx@NGr-C of azepine graphene shell, catalytic dehydrogenation synthesis of quinoline class compound (Cui, X.J.；Li,Y.H.；Bachmann,S.；Scalone,M.；Surkus,A.-E.；Junge,K.；Topf,C.；Beller, M.J.Am.Chem.Soc.2015,137,10652-10658.).Above catalyst system and catalyzing has synthesized quinoline by the use of oxygen as oxidant The heterocyclic compounds such as quinoline class, but need to use the noble metal catalysts such as Ru, Ir, catalyst amount is big, and reaction product has metal Residual, and reaction temperature is higher.
In recent years, it is seen that light-catalyzed reaction has been obtained extensively because of its green, efficient, gentle method in organic synthesis field Using also being had great application prospect by visible light catalytic Tetrahydroquinolinesas dehydrogenation synthesis of quinoline class compound. Traditional photochemical catalyst is usually the complex compound of ruthenium and iridium, is coordinated with pyridine analogs, and this kind of catalyst has very under visible light Strong absorption, property is stable and has very long life cycle, but it uses noble metal, and synthesis cost is high.
The content of the invention
The technical problems to be solved by the invention are that offer is a kind of simple to operate, and rapidly and efficiently, reaction condition is gentle, urges Agent consumption is few, high income, and without the method for metal catalytic Tetrahydroquinolinesas oxidative dehydrogenation synthesis of quinoline class compound.
Solving the technical scheme that is used of above-mentioned technical problem is：Under oxygen atmosphere, by 1 shown in formula I, 2,3,4- tetra- Hydrogen quinolines, the organic photochemical catalysts of polysubstituted BODIPY, co-catalyst are dissolved in organic solvent, under visible light illumination 50~70 DEG C of stirring reactions, are isolated and purified, and obtain quinolines shown in Formula II, and reaction equation is as follows：
In Formulas I and II, R1、R2Respective independent representative hydrogen, nitro, halogen, class halogen, trifluoromethyl, C1~C10Alkyl, C5~C6Cycloalkyl, C1~C10Alkoxy, hydroxyl, carboxyl, aldehyde radical, phenyl, C1~C4Alkyl-substituted phenyl, C1~C4Alkoxy takes For any one in phenyl, halogenophenyl, naphthyl, preferably R1、R2Respective independent representative hydrogen, halogen, trifluoromethyl, C1~ C4Alkyl, C5~C6Cycloalkyl, C1~C4Any one in alkoxy, phenyl, halogenophenyl, methoxy substitution phenyl, naphthyl.
The structural formula of the above-mentioned organic photochemical catalysts of polysubstituted BODIPY is as follows：
R in formula3、R5、R6Respective independent representative hydrogen, C1~C6Alkyl, C1~C6Alkoxy, phenyl, C1~C4Alkyl replaces Phenyl, C1~C4Any one in alkoxy substituted phenyl, halogenophenyl, naphthyl, R4Represent F, Cl, phenyl, C1~C4Alkyl Substituted-phenyl, C1~C4Any one in alkoxy substituted phenyl, halogenophenyl, naphthyl, X represents appointing in H, F, Cl, Br, I Meaning is a kind of.
In the above-mentioned organic photochemical catalysts of polysubstituted BODIPY, preferably R3、R5、R6Respective independent representative hydrogen, C1~C6Alkane Base, C1~C6Any one in alkoxy, R4Represent F, phenyl, C1~C4Alkyl-substituted phenyl, C1~C4It is alkoxy substituted Any one in base, halogenophenyl, X represents Br or I.
The addition of the above-mentioned organic photochemical catalysts of polysubstituted BODIPY is preferably that 1,2,3,4- Tetrahydroquinolinesas rubs The 0.05%~0.2% of that amount.
Above-mentioned co-catalyst is tetrabutylammonium iodide, NaI, KI, I2In any one, preferably tetra-n-butyl iodate Ammonium, the addition of co-catalyst is preferably the 1%~3% of 1,2,3,4- Tetrahydroquinolinesas moles.
In above-mentioned preparation method, preferably the time of 50~70 DEG C of stirring reactions is 4~20 hours under visible light illumination.
Above-mentioned organic solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, tetrahydrofuran, 1,4- dioxies six Any one in ring, ethyl acetate, acetonitrile.
The present invention substitutes peroxide as oxidant by the use of oxygen, and no metal photocatalysts are used in the reaction, is catalyzed Agent consumption is few, high catalytic efficiency, and reaction condition is gentle, and stability and high efficiency is simple to operate, environment-friendly, and product yield is high, choosing Selecting property is good.Compared with the method described in existing synthetic technology, the characteristics of this photocatalytic system is maximum is used without metal photocatalysis Agent, catalyst amount is few, and reaction condition is gentle, rapidly and efficiently, and yield is high, environmental protection.
Embodiment
With reference to embodiment, the present invention is described in more detail, but protection scope of the present invention is not limited in these Embodiment.
Embodiment 1
The following quinoline of composite structure formula
By the organic photochemical catalysts of polysubstituted BODIPY (0.35mg, 0.0005mmol), TBAI (3.7mg, 0.01mmol), 1, 2,3,4- tetrahydroquinolines (67mg, 0.5mmol are provided by Shanghai Sa En chemical technologies Co., Ltd), DMF (5mL) is added in parallel light reaction tube, insertion oxygen ball bubbling 10 minutes, is screwed bottle stopper, 5W blue LED lamps is opened, 60 Stirring reaction 4 hours at DEG C, question response terminates, and 20mL saturated aqueous common salts are added into mixture, 20mL ethyl acetate is then used Extract in three times, collect organic phase, use anhydrous Na2SO4Dry, suction filtration, solvent is removed with Rotary Evaporators, column chromatography for separation is obtained To colourless oil liquid quinoline 50mg, its yield is 80%, and spectral data is：1H NMR(400MHz,CDCl3) δ=8.91 (dd, J=4.2,1.5Hz, 1H), 8.13 (dd, J=13.2,8.4Hz, 2H), 7.81 (d, J=8.2Hz, 1H), 7.71 (t, J= 7.7Hz, 1H), 7.54 (t, J=7.5Hz, 1H), 7.38 (dd, J=8.3,4.2Hz, 1H)；13C NMR(101MHz,CDCl3)δ =150.44,148.32,136.05,129.49,129.46,128.30,127.80,126.54,121.08.
The organic photochemical catalysts of polysubstituted BODIPY used are the following BODIPY-4 of structural formula in the present embodiment：
It is prepared according to following methods：
Step 1,2,4- dimethyl pyrroles (1163mg, 12.5mmol) are added in 500mL flasks, add and new steam dichloro Methane (250mL), stirring is lower to instill benzaldehyde (530mg, 5mmol), then is slowly added dropwise trifluoroacetic acid (50 μ L, 0.67mmol), After room temperature reaction 3 hours, 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (1135mg, 5mmol) is added under ice bath, after 10 minutes It is warmed to room temperature, after stirring 1 hour, adds triethylamine (10mL, 72mmol), after 10 minutes, addition BFEE (10mL, 81mmol), continue to react at room temperature 2 hours, reaction mixture is extracted through removing solvent, dichloromethane and saturated aqueous common salt under reduced pressure, Take organic layer through anhydrous sodium sulfate drying, crude product is separated by silica gel column chromatography, obtain red brown solid intermediate 1 (486mg), Yield is 30%.
Step 2, take 100mL flasks to be dried 2 hours in 100 DEG C of drying boxes, flask is vacuumized and is allowed to cool under state To room temperature, intermediate 1 (318mg, 1mmol) is added, and is added under the conditions of argon gas and now steams tetrahydrofuran (40mL), stirring condition Under be added dropwise under phenyl lithium (2.0mL, 4mmol), room temperature condition stir 5 minutes after, reaction is quenched with saturated aqueous common salt, second is used Acetoacetic ester extracts three times (50mL × 3), merges organic phase and uses anhydrous sodium sulfate drying, rotary evaporation removes solvent, crude product Separated by silica gel column chromatography, obtain red brown solid intermediate 2 (110mg), yield is 25%.
Step 3, addition intermediate 2 (100mg, 0.23mmol) and new steaming dichloromethane (12mL) in 50mL flasks, stir Lower addition N- N-iodosuccinimides (207mg, 0.92mmol) are mixed, after reacting at room temperature 12 hours, reaction mixture steams through decompression Except solvent, crude product is separated by silica gel column chromatography, obtains red brown solid BODIPY-4 (110mg), and yield is 64%.
Embodiment 2
In the present embodiment, the BODIPY-4 in embodiment 1 is replaced with the following BODIPY-1 of structural formula, other steps with Embodiment 1 is identical, obtains quinoline, and its yield is 50%.
Embodiment 3
In the present embodiment, the BODIPY-4 in embodiment 1 is replaced with the following BODIPY-2 of structural formula, other steps with Embodiment 1 is identical, obtains quinoline, and its yield is 77%.
Embodiment 4
In the present embodiment, the BODIPY-4 in embodiment 1 is replaced with the following BODIPY-3 of structural formula, other steps with Embodiment 1 is identical, obtains quinoline, and its yield is 76%.
Embodiment 5
In the present embodiment, by the BODIPY-4 in embodiment 1, with the following BODIPY-5 of structural formula, (its synthetic method is referred to BODIPY-4) replace, other steps are same as Example 1, obtain quinoline, its yield is 73%.
Embodiment 6
In the present embodiment, by the BODIPY-4 in embodiment 1, with the following BODIPY-6 of structural formula, (its synthetic method is referred to BODIPY-4) replace, other steps are same as Example 1, obtain quinoline, its yield is 83%.
Embodiment 7
In the present embodiment, by the BODIPY-4 in embodiment 1, with the following BODIPY-7 of structural formula, (its synthetic method is referred to BODIPY-4) replace, other steps are same as Example 1, obtain quinoline, its yield is 74%.
Embodiment 8
In the present embodiment, by the BODIPY-4 in embodiment 1, with the following BODIPY-8 of structural formula, (its synthetic method is referred to BODIPY-4) replace, other steps are same as Example 1, obtain quinoline, its yield is 84%.
Embodiment 9
The following 2- methylquinolines of composite structure formula
In the present embodiment, with the 2- methyl isophthalic acids of equimolar amounts, 1,2,3,4- in 2,3,4- tetrahydroquinoline alternative embodiments 1 Tetrahydroquinoline, other steps are same as Example 1, obtain colourless oil liquid 2- methylquinolines, and its yield is 74%, wave spectrum number According to for：1H NMR(400MHz,CDCl3) δ=8.02 (dd, J=8.4,3.3Hz, 2H), 7.75 (d, J=8.1Hz, 1H), 7.71- 7.62 (m, 1H), 7.46 (t, J=7.5Hz, 1H), 7.26 (d, J=8.4Hz, 1H), 2.74 (s, 3H)；13C NMR(101MHz, CDCl3) δ=158.98,147.88,136.15,129.41,128.64,127.48,126.48,125.65,121.99, 25.38。
Embodiment 10
The following 2- phenylchinolines of composite structure formula
In the present embodiment, with 2- phenyl -1,2 of equimolar amounts, 1,2,3,4- in 3,4- tetrahydroquinoline alternative embodiments 1 Tetrahydroquinoline, the reaction time extends to 8 hours, and other steps are same as Example 1, obtains white solid 2- phenylchinolines, its Yield is 83%, and spectral data is：1H NMR(400MHz,CDCl3) δ=8.26-8.14 (m, 4H), 7.89 (d, J=8.6Hz, 1H), 7.83 (dd, J=8.1,0.9Hz, 1H), 7.74 (ddd, J=8.4,6.9,1.4Hz, 1H), 7.54 (tdd, J=6.9, 3.0,1.1Hz,3H),7.50-7.44(m,1H)；13C NMR(101MHz,CDCl3) δ=157.46,148.39,139.79, 136.84,129.84,129.73,129.39,128.92,127.66,127.54,127.27,126.36,119.09。
Embodiment 11
The following 2- of composite structure formula (4- methoxybenzenes)-quinoline
In the present embodiment, with the tetrahydroquinoline alternative embodiments 1 of 2- (4- methoxybenzenes) -1,2,3,4- of equimolar amounts 1,2,3,4- tetrahydroquinoline, the reaction time extends to 8 hours, and other steps are same as Example 1, obtains faint yellow solid 2- (4- methoxybenzenes)-quinoline, its yield is 89%, and spectral data is：1H NMR(400MHz,CDCl3) δ=8.15 (dt, J= 4.6,3.7Hz, 4H), 7.80 (t, J=9.0Hz, 2H), 7.71 (ddd, J=8.4,7.0,1.3Hz, 1H), 7.53-7.46 (m, 1H),7.09-7.00(m,2H),3.87(s,3H)；13C NMR(101MHz,CDCl3) δ=160.84,156.91,148.32, 136.65,132.26,129.60,129.55,128.91,127.48,126.93,125.93,118.55,114.24,55.40。
Embodiment 12
The following 2- of composite structure formula (4- bromobenzenes)-quinoline
In the present embodiment, with 1,2 in the tetrahydroquinoline alternative embodiments 1 of 2- (4- bromobenzenes) -1,2,3,4- of equimolar amounts, 3,4- tetrahydroquinolines, the reaction time extends to 8 hours, and other steps are same as Example 1, and the reaction time is 8 hours, obtains white Color solid 2- (4- bromobenzenes)-quinoline, its yield is 87%, and spectral data is：1H NMR(400MHz,CDCl3) δ=8.16 (dd, J =8.4,5.1Hz, 2H), 8.03 (d, J=8.4Hz, 2H), 7.83-7.70 (m, 3H), 7.63 (dd, J=8.8,2.0Hz, 2H), 7.53 (t, J=7.5Hz, 1H)；13C NMR(101MHz,CDCl3) δ=156.03,148.28,138.52,136.99, 132.00,129.88,129.76,129.12,127.53,127.28,126.55,123.97,118.50。
Embodiment 13
The following 2- of composite structure formula (2- naphthyls)-quinoline
In the present embodiment, with 1,2 in the tetrahydroquinoline alternative embodiments 1 of 2- (2- naphthyls) -1,2,3,4- of equimolar amounts, 3,4- tetrahydroquinolines, the reaction time extends to 6 hours, obtains white solid 2- (2- naphthyls)-quinoline, and its yield is 90%, ripple Modal data is：1H NMR(400MHz,CDCl3) δ=8.63 (s, 1H), 8.39 (dd, J=8.6,1.8Hz, 1H), 8.25 (d, J= 8.5Hz, 2H), 8.02 (dd, J=9.7,6.1Hz, 3H), 7.91 (dd, J=6.0,3.4Hz, 1H), 7.85 (dd, J=8.1, 1.2Hz, 1H), 7.76 (ddd, J=8.2,7.0,1.3Hz, 1H), 7.58-7.52 (m, 3H)；13C NMR(101MHz,CDCl3)δ =157.21,148.43,137.02,136.86,133.92,133.56,129.80,129.78,128.89,128.64, 127.79,127.56,127.28,127.20,126.77,126.39,125.13,119.21。
Embodiment 14
The following 3- methylquinolines of composite structure formula
In the present embodiment, with the 3- methyl isophthalic acids of equimolar amounts, 1,2,3,4- in 2,3,4- tetrahydroquinoline alternative embodiments 1 Tetrahydroquinoline, other steps are same as Example 1, obtain colourless oil liquid 3- methylquinolines, and its yield is 70%, wave spectrum number According to for：1H NMR(400MHz,CDCl3) δ=8.74 (s, 1H), 8.06 (d, J=8.3Hz, 1H), 7.86 (s, 1H), 7.70 (d, J =8.0Hz, 1H), 7.61 (t, J=7.5Hz, 1H), 7.48 (t, J=7.3Hz, 1H), 2.47 (s, 3H)；13C NMR(101MHz, CDCl3) δ=152.37,146.52,134.66,130.45,129.13,128.43,128.12,127.13,126.53, 18.72。
Embodiment 15
The following 3- normal-butyl quinoline of composite structure formula
In the present embodiment, with 3- normal-butyls -1,2 of equimolar amounts, 1,2,3 in 3,4- tetrahydroquinoline alternative embodiments 1, 4- tetrahydroquinolines, other steps are same as Example 1, obtain colourless oil liquid 3- normal-butyl quinoline, and its yield is 88%, ripple Modal data is：1H NMR(400MHz,CDCl3) δ=8.78 (d, J=1.9Hz, 1H), 8.07 (d, J=8.4Hz, 1H), 7.91 (d, J=1.3Hz, 1H), 7.77 (dd, J=8.1,1.0Hz, 1H), 7.65 (ddd, J=8.4,6.9,1.4Hz, 1H), 7.58- 7.46 (m, 1H), 2.85-2.73 (m, 2H), 1.71 (t, J=7.7Hz, 2H), 1.42 (dq, J=14.6,7.3Hz, 2H), 0.96 (t, J=7.3Hz, 3H)；13C NMR(101MHz,CDCl3) δ=152.26,146.88,135.46,134.17,129.25, 128.56,128.30,127.38,126.58,33.34,33.00,22.35,13.97。
Embodiment 16
The following 3- cyclohexyl quinoline of composite structure formula
In the present embodiment, with 3- cyclohexyl -1,2 of equimolar amounts, 1,2,3 in 3,4- tetrahydroquinoline alternative embodiments 1, 4- tetrahydroquinolines, other steps are same as Example 1, obtain yellow thick liquid 3- cyclohexyl quinoline, and its yield is 84%, wave spectrum Data are：1H NMR(400MHz,CDCl3) δ=8.82 (d, J=2.1Hz, 1H), 8.07 (d, J=8.5Hz, 1H), 7.91 (d, J =2.1Hz, 1H), 7.78 (dd, J=8.2,1.1Hz, 1H), 7.65 (ddd, J=8.4,6.9,1.5Hz, 1H), 7.51 (ddd, J =8.2,7.0,1.2Hz, 1H), 2.73 (tt, J=11.7,3.3Hz, 1H), 2.05-1.95 (m, 2H), 1.94-1.86 (m, 2H),1.86-1.77(m,1H),1.61-1.40(m,4H),1.39-1.28(m,1H)；13C NMR(101MHz,CDCl3) δ= 151.57,147.02,140.45,132.33,129.17,128.56,128.39,127.57,126.53,42.13,34.25, 26.84,26.09。
Embodiment 17
The following 3- phenylchinolines of composite structure formula
In the present embodiment, with 3- phenyl -1,2 of equimolar amounts, 1,2,3,4- in 3,4- tetrahydroquinoline alternative embodiments 1 Tetrahydroquinoline, other steps are same as Example 1, obtain faint yellow solid 3- phenylchinolines, and its yield is 76%, spectral data For：1H NMR(400MHz,CDCl3) δ=9.19 (d, J=2.2Hz, 1H), 8.30 (d, J=2.1Hz, 1H), 8.15 (d, J= 8.4Hz, 1H), 7.88 (d, J=8.1Hz, 1H), 7.77-7.68 (m, 3H), 7.62-7.49 (m, 3H), 7.47-7.41 (m, 1H)；13C NMR(101MHz,CDCl3) δ=150.01,147.42,137.96,133.92,133.29,129.45,129.31, 129.24,128.17,128.09,128.07,127.50,127.07。
Embodiment 18
The following 4- methylquinolines of composite structure formula
In the present embodiment, with the 4- methyl isophthalic acids of equimolar amounts, 1,2,3,4- in 2,3,4- tetrahydroquinoline alternative embodiments 1 Tetrahydroquinoline, other steps are same as Example 1, obtain colourless oil liquid 4- methylquinolines, and its yield is 76%, wave spectrum number According to for：1H NMR(400MHz,CDCl3) δ=8.78 (d, J=4.3Hz, 1H), 8.11 (d, J=8.4Hz, 1H), 8.00 (d, J= 8.4Hz, 1H), 7.71 (t, J=7.6Hz, 1H), 7.57 (t, J=7.6Hz, 1H), 7.30-7.19 (m, 1H), 2.71 (s, 3H) ；13C NMR(101MHz,CDCl3) δ=150.25,148.06,144.38,130.09,129.18,128.36,126.36, 123.89,121.93,18.73。
Embodiment 19
The following 6- methylquinolines of composite structure formula
In the present embodiment, with the 6- methyl isophthalic acids of equimolar amounts, 1,2,3,4- in 2,3,4- tetrahydroquinoline alternative embodiments 1 Tetrahydroquinoline, other steps are same as Example 1, obtain colourless oil liquid 6- methylquinolines, and its yield is 65%, wave spectrum number According to for：1H NMR(400MHz,CDCl3) δ=8.83 (d, J=4.1Hz, 1H), 8.01 (dd, J=15.8,8.4Hz, 2H), 7.53 (d, J=10.4Hz, 2H), 7.32 (ddd, J=8.1,4.1,1.9Hz, 1H), 2.51 (s, 3H)；13C NMR(101MHz, CDCl3) δ=149.53,146.92,136.36,135.33,131.72,129.12,128.32,126.58,121.05, 21.55。
Embodiment 20
The following 6- chloroquinolines of composite structure formula
In the present embodiment, with 1,2,3,4- tetra- in the tetrahydroquinoline alternative embodiments 1 of the 6- of equimolar amounts chloro- 1,2,3,4- Hydrogen quinoline, other steps are same as Example 1, obtain yellow oily liquid 6- chloroquinolines, and its yield is 78%, spectral data For：1H NMR(400MHz,CDCl3) δ=8.90 (dd, J=4.2,1.6Hz, 1H), 8.05 (t, J=9.9Hz, 2H), 7.80 (d, J=2.3Hz, 1H), 7.65 (dd, J=8.9,2.3Hz, 1H), 7.42 (dd, J=8.3,4.2Hz, 1H)；13C NMR(101MHz, CDCl3)δ150.70,146.74,135.19,132.37,131.22,130.49,128.91,126.49,121.99。
Embodiment 21
The following 6- bromoquinolines of composite structure formula
In the present embodiment, with 1,2,3,4- tetra- in the tetrahydroquinoline alternative embodiments 1 of the 6- of equimolar amounts bromo- 1,2,3,4- Hydrogen quinoline, other steps are same as Example 1, obtain yellow oily liquid 6- bromoquinolines, and its yield is 75%, spectral data For：1H NMR(400MHz,CDCl3) δ=8.92 (dd, J=4.2,1.6Hz, 1H), 8.07 (dd, J=8.3,1.3Hz, 1H), 8.02-7.93 (m, 2H), 7.78 (dd, J=9.0,2.2Hz, 1H), 7.42 (dd, J=8.3,4.2Hz, 1H)；13C NMR (101MHz,CDCl3) δ=150.84,146.96,135.12,133.04,131.34,129.89,129.45,121.98, 120.54。
Embodiment 22
The following 7- Trifluoromethylquinocarboxylics of composite structure formula
In the present embodiment, with the 7- Trifluoromethyl-1s of equimolar amounts, 1,2 in 2,3,4- tetrahydroquinoline alternative embodiments 1, 3,4- tetrahydroquinolines, the reaction time extends to 10 hours, and other steps are same as Example 1, obtains white solid 7- fluoroforms Base quinoline, its yield is 79%, and spectral data is：1H NMR(400MHz,CDCl3) δ=9.03 (dd, J=4.2,1.7Hz, 1H), 8.43 (s, 1H), 8.23 (d, J=8.3Hz, 1H), 7.96 (d, J=8.5Hz, 1H), 7.73 (dd, J=8.5,1.6Hz, 1H), 7.53 (dd, J=8.3,4.3Hz, 1H)；13C NMR(101MHz,CDCl3) δ=151.88,147.38,136.00, 131.77 (t, J=67.9Hz), 129.79,129.13,127.50 (d, J=4.4Hz), 125.36,123.00,122.35 (d, J =2.9Hz).
Embodiment 23
The following 8- methylquinolines of composite structure formula
In the present embodiment, with the 8- methyl isophthalic acids of equimolar amounts, 1,2,3,4- in 2,3,4- tetrahydroquinoline alternative embodiments 1 Tetrahydroquinoline, other steps are same as Example 1, obtain colourless oil liquid 8- methylquinolines, and its yield is 70%, wave spectrum number According to for：1H NMR(400MHz,CDCl3) δ=8.94 (dd, J=4.1,1.7Hz, 1H), 8.11 (dd, J=8.2,1.7Hz, 1H), 7.65 (d, J=8.1Hz, 1H), 7.55 (d, J=6.9Hz, 1H), 7.47-7.33 (m, 2H), 2.82 (s, 3H)；13C NMR (101MHz,CDCl3) δ=149.31,147.43,137.13,136.34,129.66,128.31,126.33,125.92, 120.88,18.20。
Embodiment 24
The following 2,6- dimethyl quinolines of composite structure formula
In the present embodiment, with 2,6- dimethyl -1,2 of equimolar amounts, 1,2 in 3,4- tetrahydroquinoline alternative embodiments 1, 3,4- tetrahydroquinolines, other steps are same as Example 1, obtain white solid 2,6- dimethyl quinolines, and its yield is 77%, ripple Modal data is：1H NMR(400MHz,CDCl3) δ=7.95 (d, J=8.4Hz, 1H), 7.91 (d, J=8.5Hz, 1H), 7.51 (dd, J=10.5,1.8Hz, 2H), 7.24 (d, J=8.4Hz, 1H), 2.72 (s, 3H), 2.51 (s, 3H)；13C NMR (101MHz,CDCl3) δ=158.06,146.51,135.61,135.44,131.71,128.37,126.55,126.45, 122.03,25.34,21.54。
Embodiment 25
The following 2- methyl -6- bromoquinolines of composite structure formula
In the present embodiment, with 1 in the tetrahydroquinoline alternative embodiments 1 of 2- methyl -6- bromo- 1,2,3,4- of equimolar amounts, 2,3,4- tetrahydroquinolines, the reaction time extends to 10 hours, and other steps are same as Example 1, obtain white solid 2- methyl- 6- bromoquinolines, its yield is 91%, and spectral data is：1H NMR(400MHz,CDCl3) δ=7.92 (d, J=8.5Hz, 1H), 7.90 (d, J=2.2Hz, 1H), 7.86 (d, J=9.0Hz, 1H), 7.72 (dd, J=9.0,2.2Hz, 1H), 7.28 (d, J= 8.4Hz,1H),2.71(s,3H)；13C NMR(101MHz,CDCl3) δ=159.58,146.53,135.16,132.85, 130.50,129.57,127.67,122.89,119.41,25.45。

Claims (8)

1. a kind of method of visible light catalytic Tetrahydroquinolinesas oxidative dehydrogenation synthesis of quinoline class compound, its feature exists In：Under oxygen atmosphere, by 1 shown in formula I, 2,3,4- Tetrahydroquinolinesas, the organic photochemical catalysts of polysubstituted BODIPY, Co-catalyst is dissolved in organic solvent, and 50~70 DEG C of stirring reactions, are isolated and purified under visible light illumination, obtains quinoline shown in Formula II Quinoline class compound；
In Formulas I and II, R1、R2Respective independent representative hydrogen, nitro, halogen, class halogen, trifluoromethyl, C1~C10Alkyl, C5~C6 Cycloalkyl, C1~C10Alkoxy, hydroxyl, carboxyl, aldehyde radical, phenyl, C1~C4Alkyl-substituted phenyl, C1~C4It is alkoxy substituted Any one in base, halogenophenyl, naphthyl；
The structural formula of the above-mentioned organic photochemical catalysts of polysubstituted BODIPY is as follows：
R in formula3、R5、R6Respective independent representative hydrogen, C1~C6Alkyl, C1~C6Alkoxy, phenyl, C1~C4Alkyl substituted benzene Base, C1~C4Any one in alkoxy substituted phenyl, halogenophenyl, naphthyl, R4Represent F, Cl, phenyl, C1~C4Alkyl takes For phenyl, C1~C4Any one in alkoxy substituted phenyl, halogenophenyl, naphthyl, X represents any in H, F, Cl, Br, I It is a kind of；
Above-mentioned co-catalyst is tetrabutylammonium iodide, NaI, KI, I2In any one.
2. visible light catalytic Tetrahydroquinolinesas oxidative dehydrogenation synthesis of quinoline class compound according to claim 1 Method, it is characterised in that：Described R1、R2Respective independent representative hydrogen, halogen, trifluoromethyl, C1~C4Alkyl, C5~C6Cycloalkanes Base, C1~C4Any one in alkoxy, phenyl, halogenophenyl, methoxy substitution phenyl, naphthyl.
3. visible light catalytic Tetrahydroquinolinesas oxidative dehydrogenation synthesis of quinoline class chemical combination according to claim 1 or 2 The method of thing, it is characterised in that：R3、R5、R6Respective independent representative hydrogen, C1~C6Alkyl, C1~C6It is any one in alkoxy Kind, R4Represent F, phenyl, C1~C4Alkyl-substituted phenyl, C1~C4Any one in alkoxy substituted phenyl, halogenophenyl, X Represent Br or I.
4. visible light catalytic Tetrahydroquinolinesas oxidative dehydrogenation synthesis of quinoline class compound according to claim 3 Method, it is characterised in that：The addition of the organic photochemical catalysts of polysubstituted BODIPY is 1,2,3,4- tetrahydro chinolines chemical combination The 0.05%~0.2% of thing mole.
5. visible light catalytic Tetrahydroquinolinesas oxidative dehydrogenation synthesis of quinoline class compound according to claim 1 Method, it is characterised in that：The addition of the co-catalyst for 1,2,3,4- Tetrahydroquinolinesas moles 1%~ 3%.
6. visible light catalytic Tetrahydroquinolinesas oxidative dehydrogenation synthesis of quinoline class compound according to claim 5 Method, it is characterised in that：Described co-catalyst is tetrabutylammonium iodide.
7. visible light catalytic Tetrahydroquinolinesas oxidative dehydrogenation synthesis of quinoline class compound according to claim 1 Method, it is characterised in that：The time of 50~70 DEG C of stirring reactions is 4~20 hours under visible light illumination.
8. visible light catalytic Tetrahydroquinolinesas oxidative dehydrogenation synthesis of quinoline class compound according to claim 1 Method, it is characterised in that：Described organic solvent be N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, tetrahydrofuran, 1, Any one in 4- dioxane, ethyl acetate, acetonitrile.
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CN108017579A (en) * 2017-11-22 2018-05-11 河南大学 A kind of method of visible ray concerted catalysis Tetrahydroquinolinesas oxidative dehydrogenation synthesis of quinoline class compound
CN108084089A (en) * 2017-12-08 2018-05-29 华南农业大学 A kind of 2- alkylamine quinolines for preventing Candida albicans and preparation method and application
CN110639567A (en) * 2019-10-10 2020-01-03 浙江工业大学 Carbon-supported ruthenium phosphide nanocluster bifunctional catalyst and preparation method and application thereof
CN113444041A (en) * 2021-06-29 2021-09-28 安徽理工大学 Method for synthesizing polysubstituted quinoline compound through photocatalysis
CN115626889A (en) * 2022-10-17 2023-01-20 南京工业大学 Organic chemical conversion method for oxidative dehydrogenation of nitrogen-containing heterocyclic compound

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Publication number Priority date Publication date Assignee Title
CN108017579A (en) * 2017-11-22 2018-05-11 河南大学 A kind of method of visible ray concerted catalysis Tetrahydroquinolinesas oxidative dehydrogenation synthesis of quinoline class compound
CN108017579B (en) * 2017-11-22 2021-01-29 河南大学 Method for synthesizing quinoline compound by oxidative dehydrogenation of tetrahydroquinoline compound under synergistic catalysis of visible light
CN108084089A (en) * 2017-12-08 2018-05-29 华南农业大学 A kind of 2- alkylamine quinolines for preventing Candida albicans and preparation method and application
CN108084089B (en) * 2017-12-08 2020-10-23 华南农业大学 2-alkylamine quinoline compound for preventing and treating candida albicans as well as preparation method and application thereof
CN110639567A (en) * 2019-10-10 2020-01-03 浙江工业大学 Carbon-supported ruthenium phosphide nanocluster bifunctional catalyst and preparation method and application thereof
CN113444041A (en) * 2021-06-29 2021-09-28 安徽理工大学 Method for synthesizing polysubstituted quinoline compound through photocatalysis
CN113444041B (en) * 2021-06-29 2023-10-03 安徽理工大学 Method for synthesizing polysubstituted quinoline compound by photocatalysis
CN115626889A (en) * 2022-10-17 2023-01-20 南京工业大学 Organic chemical conversion method for oxidative dehydrogenation of nitrogen-containing heterocyclic compound
CN115626889B (en) * 2022-10-17 2024-04-30 南京工业大学 Organic chemical conversion method for oxidative dehydrogenation of nitrogen-containing heterocyclic compound

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